KR101266564B1 - Positive type radiation sensitive resin composition for production of plated shaped body transfer film and method for producing plated shaped body - Google Patents

Abstract

The positive radiation-sensitive resin composition for producing a plated sculpture according to the present invention is a polymer having a structural unit and a crosslinked structure having an acid dissociable functional group that dissociates with (A) an acid to generate an acidic functional group, and (B) radiation-sensitive It is characterized by containing an acid generator and (C) organic solvent. This positive radiation-sensitive resin composition is excellent in sensitivity, resolution, and the like, and is excellent in adhesion to a substrate, does not generate residue in the opening after development, and can suppress cracking of the resin film after plating. Indentation of the plating into the resin film can be suppressed.

Plating moldings, positive radiation-sensitive resin composition

Description

POSITIVE TYPE RADIATION SENSITIVE RESIN COMPOSITION FOR PRODUCTION OF PLATED SHAPED BODY, TRANSFER FILM AND METHOD FOR PRODUCING PLATED SHAPED BODY}

[Patent Document 1] Japanese Unexamined Patent Publication No. 2000-250210

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-281862

[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-281863

The present invention relates to a positive radiation-sensitive resin composition, a transfer film using the composition, and a method for producing a plated molding, which are preferable for the production of a plated sculpture.

Recently, with the miniaturization of integrated circuit devices, there has been a rapid progress in the integration of large-scale integrated circuits (LSIs) and application specific integrated circuits (ASICs) suitable for specific applications. Therefore, multi-pin thin film mounting for mounting an LSI in an electronic device is required, and bare chip mounting by a tape automated bonding (TAB) method, a flip chip method, etc. has been adopted. In such a multi-pin thin film mounting method, as a terminal for a connection, it was necessary to arrange | position the projection electrode 10 micrometers or more called bumps with high precision on a board | substrate.

Such bumps were usually processed in the following order. First, after laminating | stacking the barrier metal used as a conductive layer on the wafer in which the LSI element was processed, the radiation sensitive resin composition (so-called resist) is apply | coated and dried. Subsequently, radiation is irradiated (hereinafter, referred to as "exposure") through a mask so that a part which forms a bump is opened, and it develops and a pattern is formed. Using this pattern as a mold, electrode materials such as gold and copper are deposited by electrolytic plating. Subsequently, after peeling off the resin portion, the barrier metal is removed by etching to form bumps. After that, the chip is cut out of the wafer in a square shape and transferred to a packaging process such as TAB or a mounting process such as flip chip.

In the series of bump processing steps described above, the following characteristics are required for the resist.

(1) A coating film having a uniform thickness of 20 µm or more can be formed.

(2) High resolution to cope with narrow pitch of bumps.

(3) The side wall of the pattern to be a mold is close to the vertical, and the pattern is faithful to the mask dimension.

(4) In order to raise the production efficiency of a process, it is highly sensitive and excellent in developability.

(5) Having good wettability with respect to plating liquid.

(6) The resist is eluted in the plating liquid during plating so as not to deteriorate the plating liquid.

(7) It has high adhesiveness with respect to a board | substrate so that plating liquid may not seep out at the interface of a board | substrate and a resist at the time of plating.

(8) After plating, it peels easily with a peeling liquid.

Moreover, about the plating precipitate obtained, the following characteristics are required.

(9) The shape of the pattern used as a mold is faithfully transferred, and the thing faithful to a mask dimension.

As a conventional bump processing resist, a positive radiation sensitive resin composition containing a novolak resin and a naphthoquinone diazide group-containing compound as a main component was used (for example, JP-A-2000-250210 (Patent Literature) 1)). However, even if the resist containing the composition was developed, there was a problem that the pattern became a tapered shape (pure tapered) from the substrate surface toward the resist surface, so that a pattern having vertical sidewalls was not obtained. . Moreover, since the sensitivity of the resist containing the said composition is low, exposure time was long and there existed a problem that production efficiency was low. Moreover, it was not enough in terms of the resolution and the fidelity with respect to the mask dimension of the plating precipitate of a thick film | membrane.

In addition, a positive radiation-sensitive resin composition comprising, as a bump processing resist, a polymer having an acid dissociable functional group that dissociates with an acid to generate an acidic functional group, a component that generates an acid by irradiation with radiation, and other additives (See, for example, Japanese Patent Application Laid-Open No. 2001-281862 (Patent Document 2)). The resist containing these compositions was excellent in sensitivity and resolution. In addition, by adding an alkali-soluble resin having a specific structure, adhesion during gold plating was improved to prevent the plating liquid from seeping through the interface between the substrate and the resist (see Japanese Patent Laid-Open No. 2001-281863 (Patent Document 3)). . This alkali-soluble resin was also excellent in suppressing the occurrence of tearing (cracking) caused by swelling and shrinkage of the resist film by plating. However, the said resin composition containing the said alkali-soluble resin often patterns deform | transforms at the time of gold plating at the high temperature after pattern formation, and the gold plating shape obtained also becomes larger (press-in) than the pattern size. There was a problem.

The problem of the present invention is not only excellent in sensitivity, resolution and the like, but also good adhesion to the substrate, no residue is generated in the opening after development, and the occurrence of cracking of the resin film after plating can be suppressed, and the resin film of plating It is providing the manufacturing method which can form the positive radiation sensitive resin composition which can suppress the indentation to a metal, the transfer film using this composition, and the plating molding of thick film, such as bump and wiring, with good precision.

The present inventors earnestly researched in view of the said subject. As a result, when preparing a polymer having an acid dissociable functional group that dissociates with an acid to generate an acidic functional group, a crosslinked structure is formed using a compound having two or more ethylenically unsaturated double bonds, and preferably The problem has been solved by increasing the average molecular weight.

That is, the positive radiation-sensitive resin composition for producing a plated molding according to the present invention is a polymer having a structural unit and a crosslinked structure having an acid dissociable functional group that dissociates with (A) an acid to generate an acidic functional group, (B) It is characterized by containing a radioactive acid generator and (C) an organic solvent.

It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography of the said polymer (A) is 30,000-150,000, and the said polymer (A) is represented by the structural unit represented by following formula (1), and the following formula (2) It is preferable to further have at least one structural unit selected from the structural unit represented, and the structural unit represented by following formula (6).

Wherein 1, 2, and 6 of, R ¹ is a hydrogen atom or a methyl group, R ² is - (CH _{2) j} -, and (j is an integer from O to ^3), R 3 is a hydrogen atom or 1 to 4 carbon atoms Is an alkyl group, R ¹¹ is-(CH ₂ CH ₂ O) _k -or-(CH ₂ CH ₂ CH ₂ O) _k- (k is an integer from 1 to 4), and m is an integer from 1 to 4.]

It is preferable that the structural unit which has the acid dissociable functional group of the said polymer (A) is represented by following General formula (3).

[In formula 3, R <^4> is a hydrogen atom or a methyl group, R <^5> -R <^7> is respectively independently a C1-C4 alkyl group, a C4-C20 alicyclic hydrocarbon group, an aromatic group, or one or more in these groups. It is a substituted hydrocarbon group which substituted the hydrogen atom with polar groups other than a hydrocarbon group. When any two of R ⁵ to R ⁷ are an alkyl group or a substituted alkyl group, the alkyl chains may be bonded to each other to form an alicyclic hydrocarbon group or a substituted alicyclic hydrocarbon group having 4 to 20 carbon atoms.]

Moreover, it is preferable that the said polymer (A) is a copolymer obtained by making the monomer which induces the structural unit which has an acid dissociable functional group at least, and the monomer which has 2 or more ethylenically unsaturated double bond react.

It is preferable that the positive radiation sensitive resin composition for manufacture of the plating molding of this invention contains a component (B) in 0.1-20 weight part with respect to 100 weight part of said components (A), It is preferable to further contain alkali-soluble resin (D), and it is also preferable to contain an acid diffusion control agent further.

The (B) component is 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium perfluoro-n-octanesulfonate, 4-t- It is preferable that it is at least 1 sort (s) of compound chosen from the group which consists of butylphenyl diphenylsulfonium pyrensulfonate and 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate.

Such a positive radiation sensitive resin composition is used suitably for manufacture of bumps.

The transfer film according to the present invention is characterized by having a support film and a resin film formed on the support film by using the positive radiation-sensitive resin composition for producing the plated moldings. It is preferable that the film thickness of the said resin film is 20-200 micrometers.

The manufacturing method of the plating artifact which concerns on this invention is a process of (1) forming the resin film on the wafer which has a barrier metal layer using the positive radiation sensitive resin composition for manufacture of plating artifacts, and (2) exposing the said resin film. After the step of developing to form a pattern, (3) the step of using the pattern as a mold to precipitate electrode material by electrolytic plating, and (4) peeling off the remaining resin film, and then removing the barrier metal layer by etching. It characterized by including a process. Moreover, it is preferable that the resin film in the said process (1) is formed by transferring the resin film of the said transfer film on a wafer.

BEST MODE FOR CARRYING OUT THE INVENTION [

EMBODIMENT OF THE INVENTION Hereinafter, the positive radiation sensitive resin composition for manufacture of the plating molding which concerns on this invention, the transfer film which has a resin film which consists of the said composition, and the manufacturing method of the plating molding using these are demonstrated in detail.

[Positive radiation-sensitive resin composition for plating molding production]

The positive radiation-sensitive resin composition for producing a plated sculpture according to the present invention is a polymer having a structural unit and a crosslinked structure having an acid dissociable functional group that dissociates with (A) an acid to generate an acidic functional group, and (B) radiation-sensitive It contains an acid generator, (C) organic solvent, and other components as needed.

<Component (A)>

The component (A) which comprises the positive radiation sensitive resin composition for metal-plating molding manufacture of this invention is a polymer which has a structural unit and crosslinked structure which have an acid dissociable functional group which dissociates with an acid and produces an acidic functional group.

The composition of this invention contains the component (B) which generate | occur | produces an acid by exposure (henceforth an "acid generator"), and the acid dissociable functional group of the component and the component (A) which generate | occur | produced by exposure reacts, and is an acidic functional group. And acid dissociating substances. The decomposition reaction of such an acid dissociable functional group is promoted by heating after exposure (Post Exposure Bake: hereinafter referred to as "PEB"), and as a result, the solubility in the aqueous alkali solution of the exposed portion of the polymer increases, so that a desired pattern Can be formed with high sensitivity (i.e., low exposure amount) and high resolution.

The acid dissociable functional group is not particularly limited as long as it dissociates with an acid to produce an acidic functional group, and examples thereof include a functional group for dissociating with an acid to generate a carboxyl group or a phenolic hydroxyl group. As a structural unit which has a preferable acid dissociable functional group, what is represented by following formula (3) is mentioned.

<Formula 3>

[In formula 3, R <^4> is a hydrogen atom or a methyl group, R <^5> -R <^7> may be same or different, respectively, C1-C4 alkyl group, C4-C20 alicyclic hydrocarbon group, aromatic group, or these It is a substituted hydrocarbon group which substituted one or more hydrogen atoms in group with polar groups other than a hydrocarbon group. When any two of R ⁵ to R ⁷ are an alkyl group or a substituted alkyl group, the alkyl chains may be bonded to each other to form an alicyclic hydrocarbon group or a substituted alicyclic hydrocarbon group having 4 to 20 carbon atoms.]

The structural unit represented by the above formula (3) is derived from a monomer represented by the following formula (3a).

Wherein R 3a, R ⁴ to R ⁷ is the same meaning as R ⁴ to R ⁷ in the formula (3).

As said C1-C4 alkyl group, linear or branched may be sufficient, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl Group, t-butyl group, etc. are mentioned.

The monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and the R ⁵ to R ⁷ Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by bonding of any two alkyl chains to each other include, for example, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. group; Derived from crosslinked hydrocarbons such as adamantane, bicyclo [2.2.1] heptane, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodecane, tricyclo [5.2.1.0 ^2,6 ] decane Group; Hydrogen atoms of groups derived from these cycloalkanes or crosslinked hydrocarbons are methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t And groups substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as -butyl group.

As said aromatic group, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-chlorophenyl group, 4-t-butylphenyl group, 1-naphthyl group, benzyl group etc. are mentioned, for example.

As a polar group other than a hydrogen atom and the hydrocarbon group which can be substituted in the said substituted hydrocarbon group, For example, A hydroxyl group; A carboxyl group; Oxo group (═O group); Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group Hydroxyalkyl groups such as 4-hydroxybutyl group; Alkoxyl groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group and t-butoxy group; Cyano; Cyanoalkyl groups, such as a cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, and 4-cyanobutyl group, etc. are mentioned.

Monomers which induce the structural unit represented by the formula (3) (hereinafter referred to as "monomer (3 ')") are, for example, t-butyl (meth) acrylate and 1,1-dimethyl-propyl (meth) acryl Rate, 1,1-dimethyl-butyl (meth) acrylate, 2-cyclohexylpropyl (meth) acrylate, 1,1-dimethyl-benzyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2 -Benzyloxycarbonylethyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, 2-benzylpropyl (meth) Acrylates and the like. In this, t-butyl (meth) acrylate and 1, 1- dimethyl- propyl (meth) acrylate are preferable.

Moreover, in addition to the said monomer (3 '), the monomer which dissociates with an acid and produces | generates a phenolic hydroxyl group can also be used as a monomer which guide | induces the structural unit which has an acid dissociable functional group. Specifically, hydroxystyrenes protected by acetal groups such as p-1-methoxyethoxystyrene and p-1-ethoxyethoxystyrene, t-butoxystyrene, t-butoxycarbonyloxystyrene, and the like Can be mentioned.

These monomers may be used individually by 1 type, or may be used in combination of 2 or more type.

The polymer (A) is a monomer having a structural unit having an acid dissociable functional group (including monomer (3 ')) and a monomer having two or more ethylenically unsaturated double bonds (hereinafter, "monomer (I) ) "). These two or more ethylenically unsaturated double bonds contribute to copolymerization, and a crosslinked structure is formed in a polymer (A).

When forming a plated molding, a metal pillar is formed in the groove formed by patterning the resin film by plating. A force that grows in the transverse direction acts on the metal pillar during the deposition and deposition step. In the resin film having a weak strength, the side wall of the groove is pressed by the metal and deformed, and the final metal pillar becomes a tubular shape. However, when the positive radiation-sensitive resin composition of the present invention is used, since a crosslinked structure is formed in the resin film, a rigid resin film can be formed, and a metal column having a vertical sidewall can be formed.

Examples of the monomer (I) include trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,6-hexanediol di (meth) acrylic Rate, 2,5-dimethyl-2,5-hexanediol diacrylate, neopentylglycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2 -Ethoxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, the epoxy (meth) acrylate which added (meth) acrylic acid to the diglycidyl ether of bisphenol A. , Vis Nol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, bisphenol A di (meth) acryloyloxymethylethyl ether, tetramethylolpropane tetra (meth) Poly (meth) s such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylate is mentioned.

Moreover, a commercially available compound can also be used as it is as said monomer (I). Specific examples of commercially available compounds include Alonics M-210, M-309, M-310, M-400, M-7100, M-8030, M-8060, M-8100, and Copper. M-9050, M-240, M-245, M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 Manufacture), KAYARAD R-551, Copper R-712, Copper TMPTA, Copper HDDA, Copper TPGDA, Copper PEG400DA, Copper MANDA, Copper HX-220, Copper HX-620, Copper R-604, DPCA-20, DPCA -30, East DPCA-60, East DPCA-l20 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscot # 295, East 300, East 260, East 312, East 335HP, East 360, East GPT, East 3PA, East 400 (more than Osaka Osaka Kagaku Kogyo Co., Ltd.) is mentioned.

The said monomer (I) may be used individually by 1 type, or may be used in combination of 2 or more type. In the monomer (I), trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acryl Rate is preferred.

The polymer (A) is a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit (1)"), a structural unit represented by the following formula (2) (hereinafter also referred to as "structural unit (2)"), and It is preferable to further have at least one structural unit selected from the structural units represented by the following formula (6) (hereinafter also referred to as "structural unit (6)").

&Lt; Formula 1 >

<Formula 2>

(6)

Wherein 1, 2, and 6 of, R ¹ is a hydrogen atom or a methyl group, R ² is - (CH _{2) j} -, and (j is an integer from O to ^3), R 3 is a hydrogen atom or 1 to 4 carbon atoms Is an alkyl group, R ¹¹ is-(CH ₂ CH ₂ O) _k -or-(CH ₂ CH ₂ CH ₂ O) _k- (k is an integer from 1 to 4), and m is an integer from 1 to 4.]

The polymer (A) contains at least one structural unit selected from the structural units (1), (2) and (6), thereby improving the substrate adhesiveness of the resist and at the same time, the interface between the substrate and the resist during plating. It is effective in preventing the plating liquid from seeping out. Moreover, since the said amide component acts as a weak alkali in a coating film, the said structural unit 1 has a function which suppresses the deactivation of the acid by the amine component in an environment. Moreover, since the acidity of phenolic hydroxyl group can be changed by adjusting the kind and number of substituents contained in the said structural unit (1) and (2), the solubility of the resist with respect to alkaline developing solution can be adjusted.

The structural units (1), (2) and (6) are each a monomer represented by the following general formula (1a) (hereinafter referred to as "monomer (1 ')") and a monomer represented by the following general formula (2a) (hereinafter " Monomer (2 ') "and a monomer represented by the following formula (6a) (hereinafter referred to as" monomer (6') ").

Wherein R 1a, 2a and 6a, R ¹ to R ^3, and R ¹¹ has the same meaning as R ¹ to R ³ and R ¹¹ in the formula 1, 2 and 6.

As monomer (1 '), p-hydroxyphenyl acrylamide, p-hydroxyphenyl methacrylamide, o-hydroxyphenyl acrylamide, o-hydroxyphenyl methacrylamide, m-hydroxyphenyl acrylamide, for example. Amide, m-hydroxyphenylmethacrylamide, p-hydroxybenzylacrylamide, p-hydroxybenzylmethacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, 3,5-dimethyl-4- Hydroxybenzyl methacrylamide, 3,5-di-t-butyl-4-hydroxybenzyl acrylamide, 3,5-di-t-butyl-4-hydroxybenzyl methacrylamide, o-hydroxybenzyl acrylamide Amide-group containing vinyl compounds, such as an amide and o-hydroxybenzyl methacrylamide, are mentioned.

As monomer (2 '), p-hydroxyphenyl (meth) acrylate, o-hydroxyphenyl (meth) acrylate, m-hydroxyphenyl (meth) acrylate, p-hydroxybenzyl (meth ) Acrylate, 3,5-dimethyl-4-hydroxybenzyl (meth) acrylate, 3,5-di-tert-butyl-4-hydroxybenzyl (meth) acrylate, o-hydroxybenzyl (meth) (Meth) acrylic acid esters, such as an acrylate, are mentioned.

As monomer (6 '), For example, phenoxyalkyl (meth) acrylates, such as phenoxyethyl (meth) acrylate and phenoxypropyl (meth) acrylate; Phenoxy polyalkylene glycol (meth) acrylates, such as phenoxy polyethyleneglycol (meth) acrylate and phenoxy polypropylene glycol (meth) acrylate, are mentioned.

The said monomer (1 '), (2'), and (6 ') may be used individually by 1 type, or may be used in combination of 2 or more type. Among the monomers (1 '), (2') and (6 '), p-hydroxyphenylacrylamide, p-hydroxyphenylmethacrylamide, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 3,5-dimethyl-4-hydroxybenzyl methacrylate, p-hydroxyphenyl methacrylate, p-hydroxybenzyl methacrylate and phenoxy polyethylene glycol acrylate are preferable.

When obtaining the said polymer (A), the monomer (1 '), (2'), (6 '), the monomer which derives the structural unit which has an acid dissociable functional group, and the other monomer copolymerizable with monomer (I) ( Hereinafter, the "monomer (II)" may be copolymerized.

As such a monomer (II), o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, p-isopropenyl phenol, styrene, (alpha) -methylstyrene, p-methylstyrene, p-meth Aromatic vinyl compounds such as oxystyrene; Hetero atom-containing alicyclic vinyl compounds such as N-vinylpyrrolidone and N-vinyl caprolactam; Cyano group-containing vinyl compounds such as acrylonitrile and methacrylonitrile; Conjugated diolefins such as 1,3-butadiene and isoprene; Amide group containing vinyl compounds, such as acrylamide and methacrylamide; Carboxyl group-containing vinyl compounds such as acrylic acid and methacrylic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylic acid esters, such as acrylate, isobornyl (meth) acrylate, and tricyclo decanyl (meth) acrylate, etc. are mentioned.

The said monomer (II) may be used individually by 1 type, or may be used in combination of 2 or more type. In the said monomer (II), p-hydroxy styrene, p-isopropenyl phenol, styrene, acrylic acid, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acryl The rate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate is preferable.

The content rate of the acid dissociable functional group contained in the composition of this invention will not be specifically limited if it is a range which does not impair the effect of this invention.

When the said acid dissociable functional group originates in monomer (3 '), the structural unit derived from monomer (3') contained in the said polymer (A), monomer (1 '), (2'), (3 ' Weight ratio with the sum of the structural units derived from the following formulas, (6 ') and (II) [monomer (3') / {monomer (1 ') + monomer (2') + monomer (3 ') + monomer (6') ) + Monomer (II)}] is usually in the range of 5/100 to 95/100, preferably 10/100 to 90/100, more preferably 20/100 to 80/100.

When the ratio of the structural unit derived from monomer (3 ') is lower than the said range, since the ratio of the acidic functional group produced | generated will become low, the solubility with respect to the alkaline developing solution of the polymer obtained may fall, and pattern formation may become difficult.

In addition, the structural unit derived from the monomer (I) contained in the said polymer (A) is a structural unit derived from monomer (1 '), (2'), (3 '), (6'), and (II). 0.1-10 weight part is preferable with respect to a total of 100 weight part of, and 0.5-5 weight part is more preferable.

When the ratio of the structural unit derived from monomer (I) is lower than the said range, a crosslinking reaction may not advance efficiently and plating tolerance may not be expressed. Moreover, when it is higher than the said range, while control of a polymerization reaction becomes difficult, the gelation or high molecular weight of resin may advance too much, and the resolution as a resist may fall remarkably.

In addition, when the said polymer (A) contains the structural unit derived from monomer (1 '), the structural unit derived from monomer (1'), monomer (1 '), (2'), (3 ') Weight ratio with the sum of the structural units derived from (6 ') and (II) [monomer (1') / {monomer (1 ') + monomer (2') + monomer (3 ') + monomer (6') + Monomer (II)}] is usually in the range of 1/100 to 50/100, preferably 3/100 to 30/100, more preferably 5/100 to 15/100.

Moreover, when the said polymer (A) contains the structural unit derived from monomer (2 '), the structural unit derived from monomer (2'), monomer (1 '), (2'), (3 ') Weight ratio with the sum of the structural units derived from (6 ') and (II) [monomer (2') / {monomer (1 ') + monomer (2') + monomer (3 ') + monomer (6') + Monomer (II)}] is usually in the range of 1/100 to 50/100, preferably 5/100 to 35/100, more preferably 15/100 to 25/100.

In addition, when the said polymer (A) contains the structural unit derived from monomer (6 '), the structural unit derived from monomer (6'), monomer (1 '), (2'), (3 ') Weight ratio with the sum of the structural units derived from (6 ') and (II) [monomer (6') / {monomer (1 ') + monomer (2') + monomer (3 ') + monomer (6') + Monomer (II)}] is usually in the range of 1/100 to 50/100, preferably 5/100 to 35/100, more preferably 15/100 to 25/100.

The polymer (A) is, for example, monomer (3 ') and monomer (I), preferably at least one monomer selected from monomers (1'), (2 ') and (6'), and Therefore, it can manufacture by the method of directly copolymerizing monomer (II). Polymerization can be performed by radical polymerization, and normal radical polymerization initiators, such as an organic peroxide, can be used as a polymerization initiator. Moreover, as a polymerization method, an emulsion polymerization method, suspension polymerization method, solution polymerization method, block polymerization method etc. are mentioned, for example, Especially solution polymerization method is preferable.

The solvent used in the solution polymerization method is not particularly limited as long as it does not react with the monomer component used and dissolves the polymer to be produced. Specifically, methanol, ethanol, n-hexane, toluene, tetrahydrofuran, 1,4-dioxane, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclo Hexanone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, gamma -butyrolactone, and the like. These solvent may be used individually by 1 type, or may mix and use 2 or more types.

The molecular weight of the said polymer (A) can be adjusted by suitably selecting superposition | polymerization conditions, such as a monomer composition, a radical polymerization initiator, the molecular weight regulator used as needed, polymerization temperature, and the like. The molecular weight of the polymer (A) is usually 30,000 to 150,000, preferably 50,000 to 100,000 in weight average molecular weight (Mw) in terms of polystyrene. When Mw of a polymer (A) exists in the said range, it is excellent in the strength of a resin film, plating tolerance, alkali solubility after exposure of a polymer, etc., and formation of a fine pattern becomes easy.

In addition, when a polymer (A) is manufactured by the solution polymerization method, the obtained polymer solution can also be used for manufacture of a positive radiation sensitive resin composition as it is, or the polymer (A) is isolate | separated from a polymer solution, and positive radiation It can also be used for the preparation of the resin composition. In this invention, a polymer (A) may be used individually by 1 type, or may be used in combination of 2 or more type.

<Component (B)>

The acid generator (B) used for this invention is a compound which generate | occur | produces an acid by exposure. By the action of this generated acid, the acid dissociable functional group present in the polymer (A) is dissociated, for example, an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is generated. As a result, the exposed portion of the resin film formed from the positive radiation-sensitive resin composition can be easily dissolved in the alkaline developer, and a positive pattern can be formed.

Examples of the acid generator (B) include onium salt compounds (including thiophenium salt compounds), halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds and the like. Can be mentioned.

As an onium salt compound, an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt, etc. are mentioned. Specifically, diphenyl iodonium trifluoro methanesulfonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluoro phosphate, di Phenyl iodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t -Butylphenyl diphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyldiphenylsulfonium pyrenesulfonate, 4-t-butylphenyldiphenylsulfonium n-dodecylbenzenesulfo Nitrate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4-t-butylphenyl diphenylsulfonium benzenesulfonate, 4,7-di-n-butoxynaphthyl tetrahydrothiope Phenium trifluoromethanesulfonate is preferred.

As a halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned, for example. Specifically, 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, or phenyl-bis (trichloromethyl) -s- Triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine (Trichloromethyl) -s-triazine derivatives such as these are preferable.

As a diazo ketone compound, a 1, 3- diketo-2- diazo compound, a diazo benzoquinone compound, a diazonaphthoquinone compound etc. are mentioned, for example. Specifically, 1,2-naphthoquinone diazide-4-sulfonic acid ester of phenols, 1,2-naphthoquinone diazide-5-sulfonic acid ester of phenol, etc. are preferable.

As a sulfonate, (beta) -keto sulfone, (beta) -sulfonyl sulfone, the (alpha)-diazo compound of these compounds, etc. are mentioned, for example. Specifically, 4-tolylphenacyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane and the like are preferable.

As a sulfonic acid compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned, for example. Specifically, benzointosylate, pyrogallol tristrifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl-p-toluenesulfonate and the like are preferable.

Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, and N- (trifluoromethylsulfonyloxy) Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -5,6-oxy-bicyclo [2.2.1] heptane- 2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthali Mead, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-meth Phenylsulfonyloxy) -5,6-oxy-bicyclo [2.2.1] heptane-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (2-tri Fluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2 -Trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) -5,6-oxy-bicyclo [2.2.1] heptane-2,3 -Dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) -5,6-oxy- Bicyclo [2.2.1] heptan-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) naphthylimide, and the like. Can be mentioned.

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and bis (p-toluenesulfonyl ) Diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl-1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, etc. Can be mentioned.

The said acid generator (B) may be used individually by 1 type, or may be used in combination of 2 or more type. In the acid generator (B), 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4 -t-butylphenyl diphenylsulfonium pyrenesulfonate and 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate are more preferable, and especially 4-t-butylphenyl. Diphenylsulfonium trifluoromethanesulfonate and 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate are preferable.

The amount of the acid generator (B) used when producing the composition of the present invention is usually 0.1 to 20 parts by weight based on 100 parts by weight of the polymer (A) from the viewpoint of securing the sensitivity, resolution, pattern shape, and the like as a resist. It is preferably in the range of 0.3 to 10 parts by weight, particularly preferably 1 to 5 parts by weight. By setting the usage-amount of the acid generator (B) to the above range, a resist having excellent sensitivity, resolution, and transparency to radiation is obtained, and a pattern of excellent shape is obtained.

&Lt; Component (C) >

The positive radiation-sensitive resin composition for producing a plated molding of the present invention is for the purpose of uniformly mixing the polymer (A), the acid generator (B), and other alkali-soluble resins and additives described below, which are blended as necessary. It can be diluted with an organic solvent (C).

As such an organic solvent, Ethylene glycol alkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Aromatic hydrocarbons such as toluene and xylene; Cyclic ethers such as dioxane; And methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-methyl Esters such as methyl butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate. These may be used individually by 1 type, or may mix and use 2 or more types.

The amount of the organic solvent (C) to be used is not particularly limited as long as the composition can be uniformly mixed in consideration of the method and application of the resin composition, but the amount of the solid content concentration of the resin composition is in the range of 20 to 65% by weight. It is preferable to use as. When the solid content concentration is lower than the above range, it is difficult to obtain a film thickness of 20 µm or more, which is preferable for the bump forming material, and when the above solid content is exceeded, the fluidity of the composition is significantly deteriorated, handling becomes difficult, and a uniform resin film is difficult to be obtained. There is a tendency.

<Other alkali-soluble resins>

Alkali-soluble resin (henceforth "other alkali-soluble resin (D)") other than the said component (A) can be added to the positive radiation sensitive resin composition for metal-plating molding manufacture of this invention as needed.

The other alkali-soluble resin (D) which can be used by this invention is resin which has 1 or more types of acidic functional groups, such as a phenolic hydroxyl group and a carboxyl group, which show affinity with alkaline developing solution, and is soluble in an alkaline developing solution. By adding such alkali-soluble resin, since control of the dissolution rate to the alkali developing solution of the resin film formed from the positive radiation sensitive resin composition becomes easier, developability can be improved further.

The other alkali-soluble resin (D) is not particularly limited as long as it is soluble in an alkaline developer, and for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, p-isopropenylphenol, and p-vinyl 1 type which has acidic functional groups, such as benzoic acid, p-carboxymethylstyrene, p-carboxymethoxystyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and cinnamic acid The polycondensation-type resin etc. which have addition polymerization type resin obtained by superposing | polymerizing the above monomer (except the said polymer (A)) and acidic functional group represented by novolak resin are mentioned.

The addition polymerization resin may be composed of only repeating units in which polymerizable unsaturated bonds of the monomer having an acidic functional group are cleaved, and as long as the resulting resin is soluble in an alkaline developer, at least one other repeating unit It may further contain.

As said other repeating unit, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, maleic anhydride, acrylonitrile, methacrylonitrile, crotonnitrile, male nitrile, phthalo Nitrile, mesaconitrile, citraconnitrile, itaconitrile, acrylamide, methacrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, 2-vinylpyridine, 3-vinyl And units derived from pyridine, 4-vinylpyridine, N-vinylaniline, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole and the like.

As said addition polymerization resin, the copolymer of poly (p-hydroxy styrene) and p-isopropenyl phenol is especially preferable from a viewpoint of the high radiation transmittance at the time of forming a resin film, and also excellent dry etching resistance. Do.

The molecular weight of the addition polymerization system resin is usually 1,000 to 200,000, preferably 5,000 to 70,000 in terms of weight average molecular weight (Mw) in terms of polystyrene.

The said polycondensation-type resin may be comprised only by the condensation type repeating unit which has an acidic functional group, and may contain another condensation type repeating unit as long as the produced resin is soluble in an alkaline developing solution.

Such polycondensed resins are, for example, one or more phenols and one or more aldehydes, together with a polycondensation component capable of forming other condensed repeat units as necessary, together with a water medium in the presence of an acidic catalyst or a basic catalyst. It can be prepared by (co) polycondensation in medium or in a mixed medium of water and a hydrophilic solvent.

As said phenols, o-cresol, m-cresol, p-cresol, 2, 3- xylenol, 2, 4- xylenol, 2, 5- xylenol, 3, 4- xylenol , 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like. Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde and the like.

The molecular weight of the polycondensation-based resin is usually 1,000 to 100,000, preferably 2,000 to 50,000 in terms of the weight average molecular weight (Mw) in terms of polystyrene.

These other alkali-soluble resins (D) may be used individually by 1 type, or may be used in combination of 2 or more type. The use amount of the said other alkali-soluble resin (D) is 200 weight part or less normally with respect to 100 weight part of polymers (A).

<Acid diffusion control agent>

In the positive radiation-sensitive resin composition for producing a plated molding of the present invention, an acid generated from an acid generator (B) is used to control diffusion in a resin film and to suppress an undesirable chemical reaction in an unexposed part. It is preferable to mix | blend a diffusion control agent. By using such an acid diffusion control agent, the storage stability of a composition is improved, the resolution as a resist is further improved, and the line width change of a pattern by the change of the time-lapse stability from exposure to PEB can be suppressed, and process stability This is very excellent.

As such an acid diffusion control agent, the nitrogen containing organic compound which basicity does not change by exposure and heating in the manufacturing process of a plated molding is preferable.

As said nitrogen-containing organic compound, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N, N, N ', N'- tetramethylethylenediamine, tetramethylene Diamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, form Amide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, Methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole , 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholine, 4-methylmorpholine, piperazine , 1,4-dimethylpiperazine, 1,4-diazabici As, and the like [2.2.2] octane. Among these, 2,4,6-tri (2-pyridyl) -S-triazine is particularly preferable. The acid diffusion control agent may be used alone, or may be used in combination of two or more thereof.

The use amount of the acid diffusion control agent is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the polymer (A). By carrying out the usage-amount of an acid diffusion control agent in the said range, the resist excellent in a sensitivity, developability, pattern shape, and dimensional fidelity is obtained.

<Surfactant>

In order to improve applicability | paintability, developability, etc., surfactant can also be added to the positive radiation sensitive resin composition for manufacture of the plating molding of this invention.

As such surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethyleneglycol dilaurate, Polyethylene glycol distearate and the like.

These surfactants may be used alone or in combination of two or more thereof. The usage-amount of the said surfactant is 2 weight part or less normally with respect to 100 weight part of said polymers (A).

<Other additives>

As another additive which can be mix | blended with the positive radiation sensitive resin composition for manufacture of the plating molding of this invention, a ultraviolet absorber, a sensitizer, a dispersing agent, a plasticizer, the thermal polymerization inhibitor for improving storage stability, antioxidant, etc. are mentioned, for example. . Among them, the ultraviolet absorber is useful because the scattered light enters the unexposed portion at the time of exposure to inhibit the photoreaction. As such an ultraviolet absorber, the compound which has a high extinction coefficient in the wavelength range of the ultraviolet-ray used for exposure is preferable. Moreover, an organic pigment can also be used for the same purpose.

In addition, in order to form a pattern with a favorable shape or to reduce the occurrence of cracking of the coating film, a terminal modified vinyl alkyl ether resin or a terminal modified polyether resin may be added.

(Vinyl alkyl ether resin)

As said terminal modified vinylalkyl ether resin, the polymer or oligomer represented by following General formula (4) is mentioned.

In formula 4, R <^8> and R <^9> is a hydroxyl group or a carboxyl group each independently, Preferably they are all hydroxyl groups. R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and the like, and preferably methyl and ethyl groups. Preferably it is an ethyl group.

By the positive radiation-sensitive resin composition containing such terminal-modified vinylalkyl ether resin, it is possible to form a pattern having a good shape and to reduce the occurrence of cracking of the coating film. In addition, by using the vinyl alkyl ether resin in which both ends are modified as mentioned above, compared with the case where the vinyl alkyl ether resin in which the terminal is not modified is improved, the compatibility with other resin components is improved, and Solubility is improved and resolution is remarkably improved.

The terminally modified vinyl alkyl ether resins are those having a flexible resinous shape from those having fluidity at room temperature depending on the degree of polymerization, and are appropriately selected and used. Therefore, n in general formula (4) is not specifically limited, Usually, it is an integer of 1 or more, Preferably it is 1-100, More preferably, it is 10-50.

The terminally modified vinylalkyl ether resin is 2 to 80 parts by weight, preferably 5 to 50 parts by weight, particularly preferably 5 to 30 parts by weight based on 100 parts by weight of the component (A) in the positive radiation-sensitive resin composition. It is contained in a negative range. When content of terminal modified vinyl alkyl ether resin exceeds the said range, the contrast of an exposed part and an unexposed part may not be obtained at the time of image development, and a pattern shape may deteriorate.

(Polyether resin)

As said terminal modified polyether resin, the polymer or oligomer represented by following General formula (5a) and / or 5b is mentioned.

When the positive radiation-sensitive resin composition contains such a terminal-modified polyether resin, it is possible to form a pattern having a good shape and to reduce the occurrence of cracking of the coating film. In addition, by using the polyether resin in which both ends are modified as mentioned above, resolution can be maintained by suppressing the solubility to a developing solution to some extent compared with the case where the polyether resin in which the terminal is not denatured is used. .

According to the degree of polymerization, the terminal-modified polyether resins are crystalline, from those having fluidity at room temperature, and are appropriately selected and used. Therefore, n in general formula (5a) and (5b) is not specifically limited, Usually, it is an integer of 1 or more, Preferably it is 1-30, More preferably, it is 10-20.

The terminally modified polyether resin is 2 to 50 parts by weight, preferably 5 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, based on 100 parts by weight of the component (A) in the positive radiation-sensitive resin composition. It is contained in the range. When content of terminal modified polyether resin exceeds the said range, the contrast of an exposed part and an unexposed part cannot be obtained at the time of image development, and a pattern shape may deteriorate.

[Transfer film]

The transfer film which concerns on this invention has a support film and the resin film formed from the positive radiation sensitive resin composition for manufacture of the said plated moldings on this support film. Such a transfer film can be manufactured by apply | coating and drying the said composition on a support film.

As a method of apply | coating the said composition, a spin coating method, a roll coating method, screen printing, an applicator method, etc. are mentioned, for example. In addition, the material of a support film is not specifically limited as long as it has the strength which can endure manufacture and use of a transfer film.

The transfer film can be used with a thickness of the resin film of 20 to 200 m. The transfer film of this invention can peel a support film, and can be set as a positive radiation sensitive resin film. The said resin film can be used for manufacture of the plating molding mentioned later similarly to the composition of this invention.

[Method of Manufacturing Plating Sculpture]

Method for producing a plated sculpture according to the present invention,

(1) a step of forming a resin film on a wafer having a barrier metal layer by using the positive radiation-sensitive resin composition for producing a plated molding;

(2) process of developing after exposing the said resin film and forming a pattern,

(3) a step of depositing an electrode material by electroplating with the above pattern as a mold, and

(4) After peeling a residual resin film, the process of removing a barrier metal layer by etching is included.

<Formation of radiation sensitive resin film>

The positive radiation-sensitive resin composition is applied to a predetermined substrate, particularly a substrate of an electronic component, and dried (removing the solvent by heating or reduced pressure, etc.), whereby a film thickness of 5 to 60 mu m, preferably 10 to 30 mu m A radioactive resin film (resist film) is formed. If the film thickness of the resist film is smaller than the above range, the thickness of the bump formed after plating may be insufficient, and if the above range is exceeded, it is difficult to form a homogeneous resin film. Moreover, the resist film can also be formed on a board | substrate by transfer etc. using the said transfer film which has a dry film-form resist film formed from the positive radiation sensitive resin composition for metal-plating molding manufacture of this invention previously. By this method, the manufacturing process can be simplified.

As a coating method on the board | substrate of the said positive radiation sensitive resin composition, methods, such as a spin coating method, a roll coating method, the screen printing method, an applicator method, can be employ | adopted, for example. Although the conditions at the time of drying (prebaking) the coating film which apply | coated positive type radiation sensitive resin composition on a board | substrate as mentioned above depend on the kind of each component in a composition, a compounding ratio, the thickness of a coating film, etc., normally It is about 5 to 60 minutes at 70-140 degreeC, Preferably it is 100-120 degreeC. If the prebaking time is too short, the adhesion state at the time of development worsens, and if it is too long, the solubility of an exposed part at the time of development worsens, and there exists a tendency which leads to the fall of the resolution.

<Radiation irradiation (exposure)>

By irradiating the ultraviolet-ray or visible light with a wavelength of 300-500 nm to the obtained resist film through the mask of a predetermined pattern, only the pattern part which forms a bump is exposed. As a source of these radiations, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halogen lamp, an argon gas laser, or the like can be used. Radiation means ultraviolet rays, visible rays, far ultraviolet rays, X rays, an electron beam, etc. here. The radiation dose varies depending on the type of each component in the composition, the compounding amount, the film thickness of the coating film and the like, but is, for example, 100 to 3,000 mJ / cm ² in the case of use of ultrahigh pressure mercury lamp.

<PEB>

After irradiation, the substrate is heat treated (PEB) in order to promote the decomposition reaction by the acid of the acid dissociable functional group in the resist film. The conditions at the time of heating vary depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, and the like, and are usually about 5 to 60 minutes at 80 to 140 ° C, preferably 90 to 120 ° C.

<Phenomena>

After the PEB, development is carried out using an alkaline aqueous solution as the developer, whereby the irradiated portion is dissolved and removed, and only the unradiated portion remains, thereby forming a desired resist pattern. The developing method is not particularly limited, and examples thereof include a solution immersion method, a dipping method, a paddle method, a spray method, and the like.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethyl Amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5 Aqueous solutions of alkalis such as -diazabicyclo [4.3.0] -5-nonene can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

Alkali-soluble in this invention means melt | dissolving in the said alkaline aqueous solution, for example, 5% aqueous solution of sodium hydroxide.

Although development time changes with kinds of each component of a composition, a compounding ratio, and the dry film thickness of a composition, it is 1 to 30 minutes normally. After image development, it is preferable to perform flowing water washing for 30 to 90 second, for example, and to dry in air drying, an oven, or spin-drying using an air gun etc.

<Electrolytic plating>

The substrate patterned by development is immersed by using various plating liquids for electrolytic plating at the same temperature and time as the plating recommended conditions, and electroplating is performed to form a plating pattern using the resist pattern as a template. The plating solution may be any plating solution, such as a gold plating solution, a solder plating solution, a copper plating solution, or a silver plating solution.

<Peel treatment>

After electrolytic plating, the resist pattern (unexposed part) which remains on a board | substrate can be peeled off by immersing a board | substrate in peeling liquid in stirring at room temperature to 80 degreeC for 1 to 10 minutes. Thereby, a projection plating pattern (bump) is obtained.

As said peeling liquid, For example, ethylene glycol alkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl amyl ketone; Aromatic hydrocarbons such as toluene and xylene; Cyclic ethers such as dioxane; And methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl methoxyacetate, 2-hydroxy-3- Esters such as methyl methyl butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate and ethyl acetoacetate. These may be used individually by 1 type, or may mix and use 2 or more types.

By going through the above steps, bumps of narrow pitch can be formed with high accuracy on the substrate.

<Reflow process>

When the bump is a solder bump, a spherical bump is further formed via the reflow step. Specifically, after resist stripping, the substrate is allowed to flow in a reflow furnace at room temperature to 500 ° C. for 1 to 60 minutes to heat-melt the solder bumps formed on the substrate to obtain a spherical solder plating pattern (bump).

[Example]

Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In addition, below, "part" and "%" are basis of weight unless there is particular notice.

<Synthesis of Polymer (A)>

Synthesis Example 1

36 g of p-isopropenylphenol, 15 g of isobornyl acrylate, 21 g of benzyl acrylate, 28 g of t-butyl acrylate and 1 g of 1,6-hexanediol diacrylate are 100 g of propylene glycol monomethyl ether And stirred to prepare a homogeneous solution. The solution was bubbled with nitrogen gas for 30 minutes, and then 3 g of 2,2-azobisisobutyronitrile (AIBN) was added to continue bubbling with nitrogen gas while maintaining the reaction temperature at 70 ° C. The polymerization was carried out for 3 hours. Thereafter, 1 g of AIBN was added thereto, followed by reaction for 3 hours. The temperature was raised to 80 ° C, followed by polymerization for 2 hours, and further reaction at 100 ° C for 1 hour. After the end of the polymerization, the reaction solution was mixed with a large amount of hexane to solidify the resulting polymer. Subsequently, after re-dissolving a polymer in tetrahydrofuran, the operation which coagulates with hexane again was repeated several times, the unreacted monomer was removed, and it dried at 50 degreeC under reduced pressure, and obtained polymer (A1).

(Weight average molecular weight)

Flow rate: 1.0 milliliter / minute, elution solvent: tetrahydrofuran, column temperature: 40 degreeC using the GPC column (2 G2000HXL, 1 G3000 HXL, and 1 G4000 HXL in series) manufactured by Tosoh Corporation. Monodisperse polystyrene was determined by gel permeation chromatography (GPC) as the standard material under the analytical conditions.

Synthesis Examples 2 to 15

Polymers (A2) to (A12) and (A15) having a crosslinked structure in the same manner as in Synthesis example 1, except that the kind and amount of the compound were changed to the compositions shown in Table 1, and a polymer containing no crosslinked structure ( A13) and (A14) were synthesized, respectively.

(a): Mitsui Chemicals p-isopropenylphenol

(b): Osaka Yuki Kogyo Co., Ltd. isobornyl acrylate

(c): benzyl acrylate produced by Osaka Yuki Kogyo Co., Ltd.

(d): Osaka Yuki Kogyo Co., Ltd. t-butyl acrylate

(e): p-hydroxyphenyl methacrylamide manufactured by Showa Kobunshi Co., Ltd.

(f): Kyoesha 1,6-hexanediol diacrylate

(g): Osaka Yuki Kogyo Co., Ltd. make 2,5-dimethyl-2,5-hexanediol diacrylate

(h): Trimethylolpropane trimethacrylate manufactured by Kyoeisha

(i): Phenoxypolyethylene glycol acrylate made by Kyoeisha

Example 1

(Preparation of positive radiation-sensitive resin composition for plating molding production)

100 parts by weight of polymer (A1), 3 parts by weight of 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate as acid generator (B) and 2,4 as acid diffusion control agent After dissolving 0.04 parts by weight of 6-tri (2-pyridyl) -s-triazine in 150 parts by weight of propylene glycol monomethyl ether as an organic solvent (C), a membrane filter manufactured by Teflon (registered trademark) having a pore diameter of 3 μm was used. Filtration gave a resin composition. In addition, 2,4,6-tri (2-pyridyl) -s-triazine was added as a 1% by weight ethyl lactate solution.

(Manufacture of Gold Sputter Board)

On the silicon wafer substrate having a diameter of 4 inches, chromium was sputtered to a thickness of about 500 mm 3, and thereafter, gold was sputtered to have a thickness of 1,000 mm 3 to form a conductive layer. Hereinafter, the board | substrate with which this conductive layer was formed is called "gold sputter substrate."

(Formation of patterns)

After apply | coating the said resin composition to the said gold sputter | substrate using a spin coater, it heated on 120 degreeC for 5 minutes on the hotplate, and formed the resin film of 25 micrometers in thickness. Subsequently, ultraviolet light of 300-1500 mJ / cm <^2> was irradiated using the ultrahigh pressure mercury lamp ("HBO" by OSRAM, output 1,000 W) through the pattern mask. The exposure amount was confirmed by the illuminance meter (what connected the probe "UV-35" (light receiver) to "UV-M10" (light meter) by Oak Seisakusho Co., Ltd.). After exposure, PEB was performed at 100 degreeC for 5 minutes on the hotplate. Subsequently, it was immersed and developed for 1 minute at room temperature using 2.38 weight% of tetramethylammonium hydroxide aqueous solution, and it water-washed and nitrogen-blown to form a pattern. Hereinafter, the board | substrate which formed this pattern is called "patterning substrate."

(Formation of plating sculpture)

As a pretreatment of electrolytic plating, the patterning substrate was subjected to an ashing treatment (output 100 W, oxygen flow rate 100 milliliters / minute, treatment time 1 minute) by an oxygen plasma to perform a hydrophilization treatment. Subsequently, this substrate was immersed in 1 liter of a non-cyanide gold plating liquid (NE Chemcat Co., Ltd. make, brand name "ECF-88K"), it was set to the plating bath temperature of 70 degreeC, and the current density of 0.8 A / dm <^2> , and it was about 30 Electrolytic plating was performed for a minute to form a bumped plated molding having a thickness of 15 to 18 µm. Subsequently, the mixture was washed with running water, blown with nitrogen gas, dried, and then immersed in N-methylpyrrolidone for 20 minutes at room temperature, and the resin film was peeled off to obtain a substrate having a plated molded product. Hereinafter, the board | substrate which has this plating sculpture is called "plating board | substrate."

(evaluation)

(1) Sensitivity

When the pattern of 40 micrometer pitch (30 micrometer width exclusion pattern / 10 micrometer width remaining pattern) was formed in the said gold sputter | substrate with the mask design dimension, the exposure amount which the dimension of the bottom part of an exclusion pattern becomes 30 micrometers is made into the optimal exposure amount. And evaluation from this optimal exposure amount. The results are shown in Table 3.

(2) resolution

On the gold sputtered substrate, two sheets of two patterns (30 μm width exclusion pattern / 10 μm width residual pattern, 32 μm width exclusion pattern / 8 μm width residual pattern) of 40 μm pitch are separately formed on the mask design dimensions. The patterning board | substrate was observed with the optical microscope and the scanning electron microscope, and the following references | standards evaluated. The results are shown in Table 3.

(Circle): A 32 micrometer width exclusion pattern / 8 micrometer width residual pattern can be resolved.

(Triangle | delta): A 30 micrometer width exclusion pattern / 10 micrometer width residual pattern can be resolved, but a 32 micrometer width exclusion pattern / 8 micrometer width residual pattern cannot be resolved.

X: The pattern of 40 micrometer pitch cannot be resolved, or cannot be resolved with favorable reproducibility.

(3) crack resistance

The patterned substrate was formed in the same manner as the above-described plated molded article, and after forming the plated molded article for bumps, the substrate was washed with water, blown with nitrogen gas, and the dried substrate (substrate not peeled off of the resin film) was placed at room temperature 23 deg. After leaving for 3 hours and 24 hours in a clean room maintained at about 45% of humidity, the substrate surface was observed with an optical microscope, and the following criteria were evaluated. The results are shown in Table 3.

(Circle): A crack does not generate | occur | produce in a residual pattern even after 24 hours.

(Triangle | delta): A crack does not generate | occur | produce in a residual pattern after 3 hours, but a crack occurs in a residual pattern after 24 hours.

X: A crack generate | occur | produces in a residual pattern after 3 hours.

Here, a "residual pattern" corresponds to a resist pattern.

(4) Shape of plating sculpture

(A) The plating board | substrate which formed the plating sculpture in the patterning board | substrate which formed the pattern of 40 micrometer pitch (30 micrometer width exclusion pattern / 10 micrometer width residual pattern) in the mask dimension was observed with the optical microscope and the scanning electron microscope, The following criteria evaluated. The results are shown in Table 3.

(Circle): The plated molded object is a thing with which the pattern shape formed from the resin film was transcribe | transferred faithfully, and press-fitting is not confirmed or 0.5 micrometer or less.

(Triangle | delta): An indentation shape is confirmed by plating molding in the range of 0.5 micrometer-1 micrometer with respect to the pattern shape formed from the resin film.

X: The indentation shape exceeding 1 micrometer is confirmed with respect to the pattern shape formed from the resin film by the plating molding.

(5) Shape of plating sculpture

(B) The plated substrate in which the plating sculpture was formed on the patterning substrate which formed the pattern of 40 micrometer pitch (30 micrometer width exclusion pattern / 10 micrometer width residual pattern) by the mask dimension was observed by the optical microscope and the scanning electron microscope, It evaluated on the basis of. The results are shown in Table 3.

(Circle): The pattern part formed from the resin film was transcribe | transferred faithfully in the bottom part of plating molding, and the trace which plating started to penetrate into the pattern bottom part is also not recognized.

X: The pattern shape formed from the resin film was not faithfully transferred to the bottom part of the plating molding, and the trace which plating began to penetrate into the pattern bottom part is confirmed.

[Examples 2 to 15]

Except having manufactured the resin composition in the composition of Table 2, it carried out similarly to Example 1, and formed the pattern, formed the plating molding, and evaluated. The results are shown in Table 3. In addition, resin (E1) is terminal modified vinyl alkyl ether resin represented by the said Formula (4) (Kyoto Hakko Chemical Co., Ltd. product "TOE-1000C"), and resin (E2) is a terminal modified poly represented by said Formula (5a). It is an ether resin ("MM-1000" by Nippon Yushi Corporation).

[Comparative Examples 1 and 2]

Except having manufactured the resin composition with the composition of Table 2, it carried out similarly to Example 1, and formed and evaluated the formation of a pattern and the plating molding. The results are shown in Table 3.

Acid Generator (B): 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate

Organic solvent (C): (C1) propylene glycol monomethyl ether

(C2) propylene glycol monomethyl ether acetate

(C3) ethyl lactate

Diffusion Controlling Agents: 2,4,6-Tri (2-pyridyl) -s-triazine

Resin (E1): Terminal modified vinyl alkyl ether resin (Kyoto Hakko Chemical Co., Ltd. product "TOE-1000C")

Resin (E2): Terminal modified polyether resin ("MM-1000" manufactured by Nippon Yushi Corporation)

Since the positive radiation-sensitive resin composition for producing a plated molding of the present invention has excellent sensitivity and resolution, a pattern to be a template for electroplating can be faithfully formed by mask dimensions, and the resin film formed from the composition is hard. Since it is difficult to deform, even in the electrolytic plating step, the shape of the pattern to be cast can be accurately transferred to form a plated sculpture that is faithful to the mask dimensions, and also has excellent adhesion to the substrate and at the same time during or after plating. The occurrence of cracking of the coating film can be reduced. Therefore, the positive radiation-sensitive resin composition for producing a plated molded article of the present invention can be used very preferably for the manufacture of plated molded articles of thick films such as bumps or wirings in integrated circuit devices (for example, LCD driver ICs).

Claims (14)

(A) a polymer having a structural unit and a crosslinked structure having an acid dissociable functional group that dissociates with an acid to generate an acidic functional group, (B) a radiation sensitive acid generator and (C) an organic solvent Containing, The polymer (A) is a copolymer formed by reacting a monomer which induces a structural unit having at least an acid dissociable functional group with a monomer having two or more ethylenically unsaturated double bonds, Monomers derived from the structural unit having an acid dissociable functional group include t-butyl (meth) acrylate, 1,1-dimethyl-propyl (meth) acrylate, 1,1-dimethyl-butyl (meth) acrylate, 2 -Cyclohexylpropyl (meth) acrylate, 1,1-dimethyl-benzyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-benzyloxycarbonylethyl (meth) acrylate, 2-methyl- 2-adamantyl (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, 2-benzylpropyl (meth) acrylate, hydroxystyrenes protected with acetal groups, t-butoxy At least one monomer selected from the group consisting of styrene and t-butoxycarbonyloxystyrene, Monomers having two or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , 1,4-butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,6-hexanediol di ( Meth) acrylate, 2,5-dimethyl-2,5-hexanediol diacrylate, neopentylglycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Epoxy which added (meth) acrylic acid to diglycidyl ether of tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and bisphenol A (Meth) acrylate, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, bisphenol A di (meth) acryloyloxymethylethyl ether, tetramethyl Olpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Positive type radiation sensitive resin composition for metal-plating moldings manufacture which is 1 or more types of monomers chosen from the group which consists of these. The positive radiation-sensitive resin composition according to claim 1, wherein the weight average molecular weight of polystyrene measured by gel permeation chromatography of the polymer (A) is 30,000 to 150,000. The at least one structural unit according to claim 1 or 2, wherein the polymer (A) is selected from a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (6). It further has a positive radiation sensitive resin composition for plating molding manufacturing. &Lt; Formula 1 >

<Formula 2>

(6)

Wherein 1, 2, and 6 of, R ¹ is a hydrogen atom or a methyl group, R ² is - (CH _{2) j} -, and (j is an integer from O to ^3), R 3 is a hydrogen atom or 1 to 4 carbon atoms Is an alkyl group, R ¹¹ is-(CH ₂ CH ₂ O) _k -or-(CH ₂ CH ₂ CH ₂ O) _k- (k is an integer from 1 to 4), and m is an integer from 1 to 4.] delete delete The positive radiation-sensitive resin composition according to claim 1 or 2, wherein the component (B) is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the component (A). The positive radiation-sensitive resin composition according to claim 1 or 2, further comprising alkali-soluble resin (D) other than the polymer (A). The positive radiation-sensitive resin composition according to claim 1 or 2, further comprising an acid diffusion control agent. The said (B) component is 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, and 4-t-butylphenyl diphenylsulfonium perfluoro-n of Claim 1 or 2 1 selected from the group consisting of -octanesulfonate, 4-t-butylphenyldiphenylsulfonium pyrenesulfonate and 4,7-di-n-butoxynaphthyl tetrahydrothiophenium trifluoromethanesulfonate Positive type radiation sensitive resin composition for manufacture of plating sculptures characterized by the above-mentioned compound. The positive radiation-sensitive resin composition according to claim 1 or 2, wherein the plating sculpture is a bump. It has a support film and the resin film formed on the said support film using the positive radiation sensitive resin composition for manufacture of the plating molding of Claim 1, The transfer film characterized by the above-mentioned. The transfer film according to claim 11, wherein the resin film has a film thickness of 20 to 200 m. (1) forming a resin film on a wafer having a barrier metal layer using the positive radiation-sensitive resin composition for producing a plated sculpture according to claim 1; (2) process of developing after exposing the said resin film and forming a pattern, (3) a step of depositing an electrode material by electroplating with the above pattern as a mold, and (4) The process of peeling a residual resin film and removing a barrier metal layer by etching Method of producing a plating sculpture comprising a. The method for producing a plated product according to claim 13, wherein the resin film in the step (1) is formed by transferring the resin film of the transfer film according to claim 11 onto a wafer.